Fluorescent dyes

ABSTRACT

Dyes of the formula   &lt;IMAGE&gt;  wherein A is -O-, -S- or -CH=CH- and X and Z are substituents, obtained from the corresponding 2-iminocoumarines by reaction with a compound of the formula   &lt;IMAGE&gt;

This application is a continuation in part of our copending applicationSer. No. 286,416, filed Sept. 5, 1972, now U.S. Pat. No. 3,904,642.

The invention relates to dyes of the formula (I): ##STR3## in which R¹is hydrogen, alkyl of one to four carbon atoms, alkyl of one to fourcarbon atoms bearing alkoxy, chlorine, bromine, carboxyl, carbalkoxy,carbamoyl or acetoxy as a substituent, cyclohexyl, benzyl or phenyl;

R² is hydrogen, alkyl of one to four carbon atoms, or alkyl of one tofour carbon atoms bearing alkoxy, chlorine, bromine, carboxyl,carbalkoxy, carbamoyl or acetoxy as a substituent;

R¹ and R² together with the adjacent nitrogen are the radical of afive-membered or six-membered heterocyclic ring;

Y is carbalkoxy, unsubstituted or substituted carbamoyl or cyano;

R is a radical of the formula: ##STR4## X is cyano or nitro; Z ishydrogen, cyano, chlorine, bromine, methylsulfonyl, ethylsulfonyl,sulfonamido or nitro;

A is hydrogen, methyl, ethyl, β-hydroxyethyl or β-hydroxypropyl;

R³ is hydrogen or methyl;

R⁴ is hydrogen, carbalkoxy, unsubstituted or substituted carbamoyl orcyano;

R⁶ is hydrogen, methyl, ethyl, chlorine, methoxy or ethoxy;

n is zero or 1; and

X⁻ is an anion.

The following are examples of substituents in addition to those alreadyspecified:

For R¹ and R² : methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,β-methoxyethyl, β-ethoxyethyl, β-acetoxyethyl, β-chloroethyl,β-carbomethoxyethyl, β-carboethoxyethyl, β-carbobutoxyethyl,β-methoxypropyl, β-ethoxypropyl, β-methoxy-γ-chloropropyl orβ-acetoxypropyl.

R¹ and R² together with the adjacent nitrogen may be for example theradical of pyrrolidine, piperidine, morpholine, piperazine orN-methylpiperazine.

Examples of specific radicals Y are: carbomethoxy, carboethoxy,carbobutoxy, carbamoyl, N-alkylcarbamoyl or N,N-dialkylcarbamoyl such asdiethylcarbamoyl, ethylcarbamoyl, butylcarbamoyl, isooctylcarbamoyl,methylcarbamoyl, dimethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoylor N-methyl-N-butylcarbamoyl, carboxanilide, cyclohexylcarbamoyl,benzylcarbamoyl, carboxypyrrolide, carboxypiperidide, carboxymorpholide,carboxypiperazide and carboxy-N-methylpiperazide.

Cyano is preferred for Y.

The same carbalkoxy and carbamoyl radicals as specified for Y may beused for R⁴.

Examples of anions X⁻ are chloride, sulfate, methosulfate, ethosulfate,acetate, p-toluenesulfonate, tetrachlorozincate and tetrafluoborate.

Dyes of formula (Ia): ##STR5## in which Y¹ is cyano or carbamoyl;

R⁵ is alkyl of one to four carbon atoms, preferably methyl or ethyl; andR has the meanings given above are of particular industrialsignificance.

R is preferably phenyl, benzimidazolyl, 3,4-dihydro-4-oxoquinazolyl orthenyl and may also be quaternized benzimidazolyl.

The new dyes have high brilliance, the shade lying within the range fromyellow to violet. They are suitable for dyeing polyamide, celluloseester, acrylonitrile polymer and polyester textile materials.

Compounds of formula (I) may be prepared by reacting an iminocoumarineof formula (II) ##STR6## with a compound of formula (III): ##STR7## andif desired quaternizing the reaction product. R, R¹, R² and Y have themeanings given above. Iminocoumarines of formula (II) are known fromGerman patent application P 21 29 565.8 and from German Laid-OpenSpecification No. 1,619,567.

The reaction may conveniently be carried out in a solvent at atemperature of from 50° to 200° C, preferably from 100° to 150° C.

Particularly suitable solvents are polar organic solvents, for exampleglycols and glycol ethers such as ethylene glycol or ethylene glycolmonomethyl ether, dimethylformamide or N-methylpyrrolidone; alsoacetanhydride, if necessary with added alkali metal acetate, glacialacetic acid or mixtures of solvents.

The following Examples illustrate the invention. Unless statedotherwise, parts and percentages referred to are by weight.

EXAMPLE 1

The dye of the formula: ##STR8## is obtained by boiling 4.75 parts of3-(p-cyanophenyl)-7-diethyl-2-iminocoumarine and 0.99 part ofmalononitrile in 45 parts of glycol monoethyl ether for 1 hour underreflux, cooling to 5° C, and subjecting the precipitate to suctionfiltration followed by washing with 10 parts of methanol. The yield ofyellow crystals is 4.5 parts. The melting point is 247° C.

EXAMPLE 2

The dye of the formula: ##STR9## or its isomer of the formula ##STR10##is obtained by boiling 5 parts of3-benzimidazolyl(2')-7-diethylamino-2-iminocoumarine and 1 part ofmalononitrile in 45 parts of glycol monoethyl ether for 90 minutes underrefux, then cooling to 5° C and suction filtering the depositedcrystals, washing them with 10 parts of methanol and drying them. Theyield of dark red crystals is 3.2 parts and the melting point is 275° C.

EXAMPLE 3

The dye of the formula: ##STR11## or its isomer of the probable formula:##STR12## is obtained by heating 5.7 parts of the dye from Example 2,2.52 parts of dimethyl sulfate and 130 parts of o-dichlorobenzene for 1hour at 120° C, then cooling to 20° C, suction filtering theprecipitate, washing it with petroleum ether and drying it.

The yield of black crystals having a melting point of 207° to 209° C is6.5 parts.

EXAMPLE 4

The dye of the formula: ##STR13## or its isomer of the formula ##STR14##is obtained by following the procedure described in Example 2 but using4.5 parts of 3-benzimidazolyl-(2')-7-dimethylamino-2-iminocoumarineinstead of 3-benzimidazolyl-(2')-7-diethylamino-2-iminocoumarine.

The yield of red crystals is 5 parts and the compound melts at 270° to272° C.

EXAMPLE 5

The dye of the formula: ##STR15## or its isomer of the probable formula##STR16## is obtained by heating 4.25 parts of the dye from Example 4with 5.6 parts of dimethyl sulfate and 130 parts of o-dichlorobenzenefor 3 hours at 120° C, then cooling to 0° C, suction filtering theprecipitate, washing it with 10 parts of petroleum ether and drying it.6 parts of black crystals are obtained having a melting point of 220° to225° C.

EXAMPLE 6

The dye of the formula: ##STR17## or the corresponding closed-ringproduct of the probable formula: ##STR18## is obtained by boiling 4.98parts of 3-benzimidazolyl-(2')-7-diethylamino-2-iminocoumarine and 1.47parts of methyl cyanoacetate in 45 parts of glycol monoethyl ether for 2hours 30 minutes under reflux, then cooling to 5° C, suction filteringthe red crystals, washing them with 10 parts of alcohol and drying them.The yield is 1.2 parts and the melting point is 240° C.

EXAMPLE 7

The dye of the formula: ##STR19## or its isomer of the formula:##STR20## is obtained by boiling 3.18 parts of3-(5'-methyl)-benzimidazolyl)-(2')-7-dimethylamino-2-iminocoumarine and0.66 parts of malononitrile in 45 parts of glycol monoethyl ether for 1hour under reflux, then cooling to 5° C, suction filtering, washing with10 parts of ethanol and drying. 3 parts of dark red crystals areobtained having a melting point of 312° C.

EXAMPLE 8

The dye of the formula: ##STR21## is obtained by boiling 3.1 parts of3-(p-nitrophenyl)-7-diethylamino-2-iminocoumarine and 0.66 part ofmalononitrile in 45 parts of glycol monoethyl ether for 1 hour underreflux, then cooling to 5° C, suction filtering the deposited substance,washing it with 10 parts of ethanol and drying it. The yield of redcrystals having a melting point of 296° C is 3 parts.

EXAMPLE 9

The dye of the formula: ##STR22## is obtained by boiling 3.28 parts of3-(5'-carbomethoxy)-thenyl-(2')-7-dimethylamino-2-iminocoumarine and0.66 part of malononitrile in 45 parts of glycol monoethyl ether for 1hour under reflux, then cooling to 5° C followed by suction filtrationand washing with 10 parts of methyl alcohol. After drying, 3 parts ofred crystals having a melting point of 244° to 246° C are obtained.

In a manner analogous to that described in the Examples the dyescharacterized in the following Table by their substituents are obtained:

    __________________________________________________________________________     ##STR23##                                                                                                    Shade                                         Ex.                                                                              R.sup.5                                                                          Y       R                 on polyester                                  __________________________________________________________________________    10 CH.sub.3                                                                         COOCH.sub.3                                                                            ##STR24##        yellow                                        11 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR25##        yellow                                        12 C.sub.2 H.sub.5                                                                  COOC.sub.4 H.sub.9                                                                     ##STR26##        yellow                                        13 C.sub.2 H.sub.5                                                                  CONH.sub.2                                                                             ##STR27##        yellow                                        14 C.sub.2 H.sub.5                                                                  CON(CH.sub.3).sub.2                                                                    ##STR28##        yellow                                        15 C.sub.2 H.sub.5                                                                  CONHC.sub.6 H.sub.5                                                                    ##STR29##        yellow                                        16 C.sub.2 H.sub.5                                                                   ##STR30##                                                                             ##STR31##        yellow                                        17 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR32##        yellow                                        18 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR33##        yellow                                        19 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR34##        yellow                                        20 C.sub.2 H.sub.5                                                                   ##STR35##                                                                             ##STR36##        yellow                                        21 C.sub.2 H.sub.5                                                                   ##STR37##                                                                             ##STR38##        yellow                                        22 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR39##        orange yellow                                 23 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR40##        orange yellow                                 24 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR41##        orange yellow                                 25 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR42##        orange yellow                                 26 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR43##        orange yellow                                 27 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR44##        orange yellow                                 28 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR45##        yellow                                        29 CH.sub.3                                                                         CN                                                                                     ##STR46##        yellow                                        30 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR47##        yellow                                        31 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR48##        yellow                                        32 C.sub.2 H.sub.5                                                                  CONHC.sub.6 H.sub.5                                                                    ##STR49##        yellow                                        33 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR50##        red                                           34 C.sub.2 H.sub.5                                                                  COOC.sub.4 H.sub.9                                                                     ##STR51##        red                                           35 C.sub.2 H.sub.5                                                                  COOC.sub.3 H.sub.7                                                                     ##STR52##        red                                           36 C.sub.2 H.sub.5                                                                  CONHCH.sub.3                                                                           ##STR53##        red                                           37 C.sub.2 H.sub.5                                                                  CON(C.sub.2 H.sub.5).sub.2                                                             ##STR54##        red                                           38 C.sub.2 H.sub.5                                                                  CON(C.sub.4 H.sub.9).sub.2                                                             ##STR55##        red                                           39 C.sub.2 H.sub.5                                                                   ##STR56##                                                                             ##STR57##        red                                           40 C.sub.2 H.sub.5                                                                  CONHCH.sub.2 C.sub.6 H.sub.5                                                           ##STR58##        red                                           41 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR59##        red                                           42 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR60##        red                                           43 C.sub.2 H.sub.5                                                                  COOC.sub.4 H.sub.9                                                                     ##STR61##        red                                           44 C.sub.2 H.sub.5                                                                   ##STR62##                                                                             ##STR63##        red                                           45 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR64##        orange                                        46 C.sub.2 H.sub.5                                                                  COOCH.sub.3                                                                            ##STR65##        orange                                        47 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR66##        orange                                        48 C.sub.2 H.sub.5                                                                  COOC.sub.4 H.sub.9                                                                     ##STR67##        orange                                        49 C.sub.2 H.sub.5                                                                   ##STR68##                                                                             ##STR69##        orange                                                                        Acrylonitrile                                                                 polymers                                      50 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR70##        violet red                                    51 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR71##        violet red                                    52 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR72##        violet red                                    53 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR73##        violet red                                    54 C.sub.2 H.sub.5                                                                  COOCH.sub.3                                                                            ##STR74##        violet red                                    55 C.sub.2 H.sub.5                                                                  COOC.sub.4 H.sub.9                                                                     ##STR75##        violet red                                    56 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR76##        yellowish red                                 57 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR77##        yellowish red                                 58 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR78##        yellowish red                                 59 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                     ##STR79##        yellowish red                                                                 Polyester                                     60 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR80##        yellow                                        61 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR81##        yellow                                        62 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR82##        yellow                                        63 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR83##        yellow                                        64 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR84##        yellow                                        65 C.sub.2 H.sub.5                                                                  CN                                                                                     ##STR85##        red                                           __________________________________________________________________________

EXAMPLE 66

The dye of the formula: ##STR86## is obtained by stirring 4.8 parts of3-(5'-carbomethoxy)-furyl-(2')-7-diethylamino-2-iminocoumarine and 0.93part of malononitrile in 45 parts of glycol monoethyl ether for twentyminutes at 120° C, then cooling to 5° C, suction filtering, washing with10 parts of methanol and drying. The yield is 1.5 parts and the meltingpoint is 167° to 168° C.

EXAMPLE 67

The dye of the formula: ##STR87## is obtained by stirring 7.1 parts of3-(5'-carbomethoxy)-thenyl-(2')-7-diethylamino-2-iminocoumarine and 1.5parts of malononitrile in 70 parts of glycol monoethyl ether for 1 hourat 135° C, then cooling to 5° C, suction filtering, washing with 10parts of methanol and drying. The yield is 6.4 parts and the meltingpoint is 218° to 220° C.

EXAMPLE 68

The dye of the formula: ##STR88## is obtained by stirring 5.7 parts of3-p-cyanophenyl-7-dimethylamino-2-iminocoumarine and 30 parts ofisobutyl cyanoacetate for 30 minutes at 150° C, then cooling to 5° C,suction filtering, washing with 10 parts of methanol and drying. Theyield is 5.5 parts and the melting point is 227° to 228° C.

EXAMPLE 69

The dye of the formula: ##STR89## is obtained analogously to Example 68from 5.7 parts of 3-p-cyanophenyl-7-dimethylamino-2-iminocoumarine and30 parts of methyl cyanoacetate. The yield is 5.1 parts and the meltingpoint is 268° to 270° C.

EXAMPLE 70

The dye of the formula: ##STR90## is obtained analogously to Example 68from 6.3 parts of 3-p-cyanophenyl-7-diethylamino-2-iminocoumarine and 30parts of isobutyl cyanoacetate. The yield is 4.9 parts and the meltingpoint is 214° to 216° C.

EXAMPLE 71

The dye of the formula: ##STR91## is obtained analogously to Example 68from 6.3 parts of 3-p-cyanophenyl-7-diethylamino-2-iminocoumarine and 30parts of ethyl cyanoacetate. The yield is 2.4 parts and the meltingpoint is 200° to 202° C.

EXAMPLe 72

The dye of the formula: ##STR92## is obtained analogously to Example 68from 6.3 parts of 3-p-cyanophenyl-7-diethylamino-2-iminocoumarine and 30parts of methyl cyanoacetate. The yield is 5 parts and the melting pointis 248° to 250° C.

EXAMPLE 73

Treatment of the dye of Example 2 with concentrated sulfuric acid:

6.5 parts of the dye from Example 2 is introduced with stirring at about20° C into 28 parts of 98% sulfuric acid and stirred for 4 hours at 20°C. The solution is then poured slowly into a mixture of 1000 parts ofwater and 1000 parts of ice. 500 parts of saturated common salt solutionis then added and the precipitated substance is suction filtered, thefilter cake, while still moist, is suspended in 1000 parts of water andwhile stirring at about 20° C the pH is adjusted with caustic sodasolution to 7.5. After stirring for 12 hours the deposited substance issuction filtered, washed with 1000 parts of water and dried. 6.4 Partsof dye having a melting point of 264° to 266° C is obtained.

EXAMPLE 74

10 Parts of2-imino-3-(3',4'-dihydro-4'-oxoquinazolin-yl-2')-7-diethylaminocoumarineis heated in 80 parts of ethyl cyanoacetate for 1 hour at 80° C and 3hours at 120° C. After cooling, the dye is suction filtered, washed withmethanol and dried. 7 parts of the dye of the formula: ##STR93## isobtained. It has a melting point of 210° to 212° C.

The dyes in which R⁵ is methyl have very similar properties; the shadeof the dyeings shows a hypsochromic shift.

    __________________________________________________________________________     ##STR94##                                                                                                                  shade on                        Ex.                                                                              R.sup.5      R.sup.5                                                                              Y         R            polyester                       __________________________________________________________________________    75 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                      CN                                                                                       ##STR95##   yellow                          76 "            "      CN                                                                                       ##STR96##   "                               77 "            "      CN                                                                                       ##STR97##   "                               78 CH.sub.3     CH.sub.3                                                                             CN                                                                                       ##STR98##   "                               79 "            "      CO.sub.2 CH.sub.3                                                                        ##STR99##   "                               80 "            "                                                                                     ##STR100##                                                                              ##STR101##  "                               81 "            "      CO.sub.2 C.sub.6 H.sub.13                                                               "            "                               82 "            "      CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                     "            "                               83 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                      CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                      ##STR102##  yellow                          84 "            "      CO.sub.2 (CH.sub.2).sub.2 OC.sub.4 H.sub.9                                              "            "                               85 C.sub.4 H.sub.9                                                                            C.sub.4 H.sub.9                                                                      CN        "            "                               86 HOCH.sub.2CH.sub.2                                                                         HOCH.sub.2 CH.sub.2                                                                  CN        "            "                               87 CH.sub.3 OCH.sub.2 CH.sub.2                                                                CH.sub.3 OCH.sub.2 CH.sub.2                                                          CN                                                                                       ##STR103##  yellow                          88 "            "      CN                                                                                       ##STR104##  "                               89 (CH.sub.2).sub.5    CN                                                                                       ##STR105##  orange yellow                   90 "                                                                                                            ##STR106##  yellow                          91 "                   CN                                                                                       ##STR107##  "                               92 (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                 CN        "            "                               93 (CH.sub.2).sub.4    CN        "            "                               94 (CH.sub.2)NH(CH.sub.2).sub.2                                                                      CN        "            "                               95                                                                                ##STR108##  "      "                                                      96 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                      CONHC.sub.2 H.sub.5                                                                     "            "                               97 "            "      CONHC.sub.6 H.sub.13                                                                    "            "                               98 "            "      CON(C.sub.2 H.sub.5).sub.2                                                              "            "                               99 "            "      CON(C.sub.4 H.sub.9).sub.2                                                              "            "                               __________________________________________________________________________

We claim:
 1. A dye of the formula ##STR109##in which: R¹ is C₁ - to C₄ -alkyl, C₂ - or C₃ -hydroxyalkyl, cyanoethyl or C₃ - to C₆ -alkoxyalkyl;R² is hydrogen, C₁ - to C₄ -alkyl or hydroxyethyl; A is --CH=CH--; X is hydrogen, cyano or nitro; Z is hydrogen, chlorine or bromine; and Y is cyano.
 2. A dye according to the formula in claim 1, in which R¹ and R² are C₁ - to C₄ -alkyl.
 3. A dye according to the formula in claim 1, in which R¹ and R² are methyl or ethyl.
 4. A dye according to the formula in claim 1, in which X is cyano or nitro and Z is hydrogen.
 5. A dye according to claim 1 of the formula ##STR110##in which R⁵ is methyl or ethyl and A is --CH=CH--.
 6. A dye according to claim 1 of the formula ##STR111## 